The present invention relates to fluoroalkylglycosiduronic acids and the corresponding lactones, to a process for their preparation and to their uses, in particular as surfactants.
Fluoro compounds are known for their surfactant properties. The most important family of these compounds is represented by anionic derivatives of the carboxylate, sulphonate, sulphate and phosphate type.
In particular, sugar-based fluoro compounds have formed the subject of much research since they offer, inter alia, excellent compatibility with human tissues. Accordingly, their applications fall essentially in the biomedical field, where they are employed to form fluorocarbon vesicles or emulsions which act as blood substitutes, contrast agents or vectorization agents and agents for the controlled release of medicinal products.
The prior art in this field includes in particular:
the article by J. G. Riess and J. Greinier Carbohydrates as Organic Raw Materials II, pp. 209-259, published by VCH (1993)! which describes fluoroalkyl sugars comprising a hydrophilic head of lucidic nature, a junction component (for example ester, ether, amide or phosphoester), a hydrocarbon spacer and a perfluoroalkyl tail; PA1 patent applications WO-A-92/05444 and WO-A-92/05445 which describe a reactant intended to immobilize a biomolecule on a solid or liquid fluorocarbon support. This reactant contains, on the one hand, fluoroalkyl groups which allow binding to the support, and, on the other hand, a reactive group on the anomeric carbon which is necessary for covalent coupling with the biomolecule; PA1 application WO-A-92/21688 which describes perfluoroalkyl and phosphorus-containing amphiphilic molecules containing in particular a radical derived from a sugar; PA1 and application WO-A-94/03468 which discloses amphiphilic molecules containing a polyhydroxylated hydrophilic part, in particular a mono- or oligosaccharide, a hydrophobic part, for example a fluorocarbon part, and a component for joining the said parts together, which is derived from an amino acid or a peptide. PA1 m is between 2 and 22, PA1 n is equal to 0 or 1, PA1 p is between 1 and 21. PA1 1 molar equivalent of a glycosiduronic acid or of a glycosiduronolactone; PA1 1 to 25 molar equivalents of an alcohol of formula R.sub.1 OH, R.sub.1 having the meaning given above, preferably 1 to 3 equivalents when an additional solvent is used and 3 to 25 equivalents when no additional solvent is used; PA1 0.01 to 2 molar equivalents of an acidic catalyst or 0.05 to 6 equivalents by weight of a resin or a clay which is acidic. PA1 one molar equivalent of fluoroalkyl fluoroalkylglycosiduronate obtained according to the mode of preparation described above; PA1 0.5 to 10 molar equivalents, preferably 1 to 3 equivalents, of a base. PA1 a solvent (0 to 20 equivalents by weight per one equivalent by weight of glycoside employed) chosen from water, alkanes such as pentane, hexane, heptane and octane, oxide ethers such as tetrahydrofuran, dioxane and ethylene glycol dimethyl ether or diethylene glycol dimethyl ether, halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane, short-chain alcohols such as methanol, ethanol, propanol, isopropanol and butanol, or longer-chain (up to 14 carbon atoms) alcohols such as octanol, decanol, dodecanol and tetradecanol and mixtures of these solvents. PA1 a phase transfer catalyst (0 to 1% by weight per 1 equivalent of glycoside employed), for example a nonionic, cationic or anionic surfactant, in particular amines and compounds containing ammonium of phosphonium ions, a crown ether, a cryptand, an amino polyether, a phosphoryl sulphoxide and a glycol ester or sorbitan ester. PA1 chromic bath additives, impermeabilizing additives in particular paper, photographic emulsion additives, polymer additives, in particular for preparing plastic films; PA1 replacements for mercury in batteries with a zinc anode; PA1 dispersion polymerization agents or emulsion polymerization agents, in particular chlorocarbon or fluorocarbon compounds, and may be involved in electrochemical processes; PA1 liquid crystals which may be used in electrooptics or in pharmacy for the formation of lamellar phases, vesicles or capsules allowing active principles to be stabilized and vectorized, and PA1 oxygen carriers in compositions for biomedical use. PA1 Nuclear magnetic resonance (NMR) PA1 Infrared (IR) spectrography; 1% KBr disc PA1 The Rf is measured by thin layer chromatography on silica (film thickness: 200 .mu.m; particle size: 5-.mu.m). The migration solvent is a 9/5 (v/v) chloroform/methanol mixture (Example 9) or ethyl acetate (Example 12). The migration spots are detected by spraying with 50% by volume sulphuric acid in water and heating at 120.degree. C. for 2 minutes. PA1 Surface tension (.gamma.CMC): measured at 25.degree. C. using a Lauda tensiometer according to the stirrup tear method (ISO standard 304) using an aqueous solution in double-distilled water. The results are expressed in mN/m. The reference compound used is a polyfluoroalkyl-betaine (Forafac 1157 marked by Elf Atochem S.A.). PA1 Critical micelle concentration (CMC): measured according to ISO standard 4311. The results are expressed in g/l.
Moreover, it is known that glycosiduronic acid derivatives are surfactants of high performance which are well tolerated by the skin and the mucous membranes. Such compounds are described, for example, in EP-A-550,276, EP-A-537,820, EP-A-532,370 and P-A-05-170,642. However, it is not taught that the abovementioned compounds can contain one or more fluoroalkyl radicals.